Chapter 11

Solution Thermodynamics:
Theory
Prof. Samir I. Abu-Eishah
Chemical Engineering
UAE University

1
Compositions

A real system usually contains a mixture of fluids.

Develop the theoretical foundation for applications of
thermodynamics to gas mixtures and liquid solutions.
Introducing
Chemical Potential
Partial Properties
Fugacity
Excess Properties
Ideal Solution

2
Auxiliary Functions

d(nU) = T d(nS) - P d(nV) = U(S,V) (6.7)

d(nH) = T d(nS) + (nV) dP = H(S,P) (6.8)
d(nA) = -P d(nV) - (nS) dT = A(V,T) (6.9)
d(nG) = (nV) dP - (nS) dT = G(P,T) (6.10)

3
11.1 Fundamental Property Relation

The basic relation connecting the Gibbs energy to

the temperature and pressure in any system:
(nG) (nG)
d(nG) dP dT (nV )dP (nS )dT (6.6)
P T ,n T P ,n

applied to a single-phase fluid in a closed system wherein

no chemical reactions occur.
Consider a single-phase, system:

(nG) (nG) (nG)

d(nG) dP dT dni
P T ,n T P ,n i ni P ,T , n
j

4

Define the chemical potential: i (nG ) (11.1)
ni P ,T ,n j

The fundamental property relation for single-phase fluid systems of constant or

variable composition:
d(nG) (nV )dP (nS )dT i dni (11.2)
i

When n = 1, dG VdP SdT dx

i
i i G G( P, T , x1 , x2 ,..., xi ,...)

G G
(11.3) V S
P T , x T P, x
(11.4) (11.5)

The Gibbs energy is expressed as a function of its canonical variables. Thus,

G
Since H = G + TS, then H G T
T P , x 5
 11.2 Chemical Potential and Phase Equilibria

Consider a closed system consisting of in

equilibrium:

d(nG) (nV ) dP (nS ) dT i dni d(nG) (nV ) dP (nS ) dT i dni

i i

nM (nM ) (nM )

d(nG) (nV )dP (nS )dT i dni i dni

i i

Mass balance:
Multiple phases at the same T and P are in dni dni
equilibrium when the chemical potential i i (11.6) 6
of each species is the same in all phases.
11.3 Partial Properties
Define the partial molar property of species i:
Types of properties:
Solution properties: M (nM )
Partial properties: Mi (11.7)
Pure-species properties: Mi ni P ,T ,n j
The chemical potential and the species molar Gibbs energy
are identical: i Gi (11.8)
For the thermodynamic property M:

nM M ( P, T , n1 , n2 ,..., ni ,...)

M M
d(nM ) n dP n dT M i dni (11.9)
P T ,n T P ,n i

Using Eq. (11.7) for M i 7

 M M
d(nM ) n dP n dT M i dni (11.9)
P T ,n T P ,n i

But ni = xi n and dni d( xi n) xi dn ndxi

M M
ndM Mdn n
dP n T dT M i ( xi dn ndxi )
P T ,n P ,n i

M M

dM
P T ,n
dP
T P ,n
dT
i
M i dxi n

M
i
xi M i dn 0

Then
M M M xi M i 0
dM dP dT M i dxi 0 and (11.11)
P T ,n T P ,n i i

Or
From (11.11) dM xi dM i M i dxi
i i
nM ni M i 0 (11.12)
Then i

M M
dP dT xi dM i 0 (11.13) Calculation of mixture
P T ,n T P ,n i properties from partial
properties 8
This is the Gibbs-Duhem equation
Partial properties in binary solution
At constant T & P, Eq. (11.13) gives x dM
i
i i 0 (11.14)
For binary system:
M M1 x2 (M1 M 2 )
M x1M1 x2 M 2
M M 2 x1 (M1 M 2 )

dM x1dM1 M1dx1 x2dM 2 M 2dx2

based on Eq. (11.14)

dM M1dx1 M 2dx2
Since x1 x2 1 then dx1 -dx2
dM
M1 M 2 M 1 M x2
dM
M 2 M x1
dM
dx1 dx1 dx1
9
(11.15) (11.16)
 Example 11.2: Graphical interpretation of equations. (11.15) and (11.16)

Tangent at x1 = 0

Tangent at x2 = 0

Figure 11.1: (a) Graphical construction of Example 11.2. (b) Infinite dilution values of partial properties

(2 ) (1 2 )
= and = 2 = 1 = 2 and 1 = + 2 = 1
1 1
1 1 0 1 10
10
 Real H-x1

Ideal H-x1

Fig. 10.1*. Schematic showing pure component and partial molar enthalpies
for a binary solution (1 and 1 ) and (2 and 2 ) 11
Example 11.3: The need arises in a laboratory for an antifreeze solution consisting
of 30 mol% methanol (1) in water (2). What volumes of pure methanol and of pure
water at 25C must be mixed to form the 2000 cm3 of the antifreeze at 25C?
The partial and pure molar volumes are:

V 1 38.632 cm 3 /mol; V1 40.727 cm 3 /mol

V 2 17.765 cm 3 /mol; V2 18.068 cm 3 /mol

Here, 1 stands for methanol and 2 for water

V x1V1 x2V2 V (0.3)(38.632) (0.7)(17.765) 24.025 cm3 /mol

n1 (0.3)(83.246) 24.974 mol

Vt 2000
n 83.246 mol
V 24.025 n2 (0.7)(83.246) 58.272 mol

V1t n1V1 (24.974)(40.727) 1017 cm3 V2t n2V2 (58.272)(18.068) 1053 cm3
See also Fig 11.2
12
 V1

V 2

Fig 11.2 Molar volumes for methanol (1) - water (2) at 25 oC and 1 atm.
13
Numerical values relate to Example 11.3
Example 11.4: The enthalpy of a binary liquid system of species 1 and 2 at fixed
T and P is given by: H 400 x 600 x x x (40 x 20 x )
1 2 1 2 1 2

Determine expressions for H1 and H 2 as functions of x1, numerical values for the
pure-species enthalpies H1 and H2, and numerical values for the partial enthalpies

at infinite dilution H1 and H 2

H 400 x1 600 x2 x1 x2 (40 x1 20 x2 ) H1 = 400 H2 = 600

at x1 = 1 at x2 = 1
x1 x2 1
H 600 180 x1 20 x13 H1 420 60 x12 40 x13 H 2 600 40 x13
dH
H1 H x2
dx1

x1 0 x1 1

J J
H1 420 H 2 640
mol mol

14
Relations among partial properties
d(nG) (nV )dP (nS )dT Gi dni (11.17)
i

Maxwell relation:
Eq. (6.16)
V S Gi (nV ) Gi (nS )

T P ,n P T ,n P T ,n ni P ,T , n j T P ,n ni P ,T , n j

Gi Gi
Vi Si
P T ,x T P ,x
(11.18) (11.19)
Similarly, dGi Vi dP Si dT
H U PV H i U i PVi 15
11.4 The Ideal-Gas Mixture Model

Gibbss theorem
A partial molar property (other than volume) of a
constituent species in an ideal-gas mixture is equal to
the corresponding molar property of the species as a
pure ideal gas at the mixture temperature but at a
pressure equal to its partial pressure in the mixture.
Vi ig Vi ig V ig RT / P (11.20)

M iig Vi ig

M iig (T , P) M iig (T , pi ) (11.21)

16
For properties that are independent of pressure:
H (T , P) H (T , pi ) H (T , P)
ig ig ig H ig yi H iig (11.25) U ig
y U
i i
ig
i i i
i i
(11.22)
For properties that depend on pressure: dSiig Rd ln P (const.T )

P P
Siig (T , P) Siig (T , pi ) R ln R ln R ln yi
pi yi P
M iig (T , P) M iig (T , pi )

(11.23) S (T , P) S (T , P) R ln yi
ig ig S ig yi Siig R yi ln yi
i i
i i

(11.26)
H iig (T , P) H iig (T , P)
Giig H iig TSiig Giig H iig TSiig RT ln yi
Siig (T , P) Siig (T , P) R ln yi

G ig yi Gi ig RT yi ln yi iig Giig Giig RT ln yi

i i

(11.27) (11.24)
RT
From integration of dGi Vi dP P dP RT d ln P
ig ig 17
Rearranging Eq. (11.26) gives
S ig yi Siig R yi ln(1 / yi )
i i

At constant T, Eq. (6.10) gives dG ig V ig dP RT dP RT d ln P

i i
P

By integration: G ig (T ) RT ln P (11.28)
i i

iig Giig Giig RT ln yi iig i (T ) RT ln yi P (11.29)

G ig yi i (T ) RT yi ln yi P
i i

(11.30)

18
11.5 Fugacity and Fugacity Coefficient

Chemical potential: (nG )

i
ni P ,T , n j

provides fundamental criterion for phase equilibria

however, the Gibbs energy, hence i, is defined in relation
to the internal energy and entropy (absolute values are
unknown).
Fugacity (See Eq. 11.28): Gi i (T ) RT ln f i (11.31)
a quantity that takes the place of i

with units of pressure

19
Gi i (T ) RT ln f i (11.31)

Giig i (T ) RT ln P (11.28)
fi
Gi Gi RT ln
ig fi
GiR RT ln i (11.33) i (11.34)
P
P
Residual Gibbs energy Fugacity coefficient

Integration of Eq. (6.49) for species i

GiR / RT ln i
P dP
ln i ( Z i 1) (const. T )
0 P
(11.35)
for species i
From virial EOS: Zi -1 = BiiP/RT
P
ln i ( Bii / RT ) dP ( BiiP / RT ) (const. T ) (11.36)
0

20
Fugacity coefficients from the generic cubic
EOS
Combination of Eq. (11.33) and eq. (6.66b) gives

ln i Zi 1 ln( Zi i ) qi Ii (11.37)

See Eq. (3.50) for i, Eq. (3.51) for qi and Eq. (6.65b) for Ii

21
VLE for pure species
For saturated vapor: Giv i (T ) RT ln f i v (11.38a)
For saturated liquid: Gil i (T ) RT ln f i l (11.38b)

fi v
G G RT ln l
i
v
i
l

fi
VLE
fi v
G G RT ln l 0
i
v
i
l
(11.40) fi

(11.41) iv il isat f i v f i l f i sat (11.39)

For a pure species coexisting liquid and vapor phases are in equilibrium
when they have the same T, P, fugacity fi and fugacity coefficient i. 22
Fugacity of a pure liquid
The fugacity of pure species i as a compressed liquid:
fi P
Gi Gisat RT ln Gi G sat
sat Vi dP (isothermal process)
f i sat i
Pi

P dP
fi 1 ln ( Z 1)
P

sat v
(11.43) ln sat
l
Vi dP i i
(11.42)
fi RT Pi sat 0 P

Since Vi l is a weak function of P, then

fi Vi l ( P Pi sat ) f i sat isat Pi sat V l

( P P sat
)
ln f i isat Pi sat exp i i
f i sat RT RT
(11.44)
The exponential term above is called the Poynting correction factor 23
Example 11.5: For H2O at 300C and for P up to 10,000 kPa (100 bar), calculate
values of fi and i from data in the steam tables and plot them vs. P.

For a state at P: Gi i (T ) RT ln f i
For a low pressure reference state (*): Gi* i (T ) RT ln f i*
A
fi
1 Hi Hi
*
fi

1
*
ln * ( Si Si )
* ln (G Gi )
Gi H i TSi
* i
fi R T fi RT
Si* 10.3450 J
At low pressure (say, 1 kPa) at 300C: f i P 1 kPa
* *
g.K

H i* 3076.8 J
g
For different values of P from 1 kPa up to the saturation pressure at 300C (i.e., P
= 8592.7 kPa), one obtains the values of fi , and hence i
At 4000 kPa and 300C: Si 6.3642 J H i 2962.0.8 J
g.K g

Values of fi and i at P > Psat: Vi l ( P Pi sat )

fi P
i
sat sat
i exp
RT
24
 f i 18.015 2962.0 3076.8
ln ( 6.3642 10.3450) 8.1917
fi *
8.314 573.15
fi
*
3,610.86
fi
f i 3610.86 f i * 3610.86 (at 1 kPa)
Thus the fugacity coefficien t at 4000 kPa is
fi
i 3610.86 / 4000 0.9028
P
Similar calculatio ns can be made at other P' s till P sat 8592.7 kPa
Vi l ( P Pi sat )
At 10,000 kPa ( P ) use f i P exp
sat
i
sat sat
i
RT
Vi l 1.403 *18.015 25.28 cm 3 /mol (at 300 o C)
f i (0.7843x8592.7) exp{25.28(10,000 8,592.7) /(8,314x573.15)}
6,789.8 kPa
f
i i 6,789.8 / 10,000 0.679
P
25
See also Fig 11.3
Check possible solution below ???
At Psat = 8592.7 kPa and T = 573.15 K:
Tr = 573.15/647.1 = 0.886;
Pr = 8592.7/(220.55x101.325) = 0.385

sat = exp (B Psat/RT); if assumed valid ????

B = (Bo + B1).R Tc/Pc
Bo = 0.083 - 0.422/Tr^1.6 = -0.4292
B1 = 0.139 - 0.172/Tr^4.2 = -0.14696
= 0.345
Bo + B1 = -0.4292 + 0.345 x -0.14696 = -0.48
B = -0.48 x 83.14 x 573.15/220.55 = -103.71
sat = exp{(-103.71 x 8592.7)/(8,314x573.15)} = 0.83147
fsat = sat Psat = 0.83147 x 8592.7 = 7,143.97 kPa

Or, sat = o + 1 = needs interpolation

26
 All properties are determined at T = 300 oC
sat o
P, kPa T , C H, J/g S, J/g. C V, ml/g ln(f/f*) f, kPa
1 6.98 3076.8 10.3450 0.0 1.0
1.0
4000 250.33 2962.0 6.3642 8.1917 3610.8446
0.9027
5000 263.01 2925.5 6.2105 8.3867 4388.5226
0.8777
6000 275.55 2885.0 6.0692 8.5398 5114.3621
0.8524
8592.7 300.00 2751.0 5.7081 1.404 8.8157 6738.9161
0.7843
10,000 310.96 6789.4430
0.6789

Vi l ( P Pi sat )
At P > Psat use fi P
i
sat sat
i exp
RT

27
 28
Fig 11.3 Fugacity and fugacity coefficient of steam at 300 oC
11.6 Fugacity and Fugacity Coefficient:
Species in Solution
For species i in a mixture of real gases or in a solution of
liquids:
i i (T ) RT ln fi (11.46)

fi = fugacity of species i in solution (replacing the species pressure)

Multiple phases at the same T and P are in equilibrium when

the fugacity of each constituent species is the same in all
phases:
fi fi ... fi

(11.47)
For two phase VLE system:
fi fi (11.48)
v l

29
The residual property: M R M M ig (6.41)

The partial residual property: M R M M ig (11.49)

i i i

Gi R Gi Giig (11.50)

i i (T ) RT ln fi
iig i (T ) RT ln yi P
fi
i ig
i RT ln
yi P

For ideal gas (nG )

i Gi
Gi R 0 ni P ,T ,n j

Gi R RT ln i (11.51)
(11.53)

f
i i 1 fi Fugacity coefficient of
fi yi P
i (11.52) 30
yi P yi P species i in solution
 The fundamental residual-property relation

nG 1 nG
d d(nG) dT
RT RT
2
RT

d(nG) (nV )dP (nS )dT i dni

i

G H TS
(11.54)
nG nV nH Gi nG
d
RT RT
dP
RT 2
dT
i RT
dni
RT
f ( P, T , ni )

G/RT as a function of its canonical variables allows evaluation of all other

thermodynamic properties, and implicitly contains complete property information.
The residual properties: (11.55) Using Eq. (11.51): (11.56)
nG R nV R nH R Gi
R
nG R nV R
d dP 2
dT i RT i or d
dn dP
nH R
dT 31
ln i dni
RT RT RT
RT RT RT 2
i
 nG R nV R nH R
R
nG R nV R nH R
dT ln i dni
Gi
d dP 2
dT dni d dP 2
RT RT RT i RT RT RT RT i

Fix T and ni: V R (G R / RT )

(11.57)
RT P T , x

Fix P and ni : HR (G R / RT )
T (11.58)
RT T P, x

Fix T and P: (nG R / RT )

ln i (11.59)
n i P ,T ,n j

32
Example 11.6: Develop a general equation for calculation of ln i values form
compressibility-factor data.

( nG R
/ RT )
ln i
ni P ,T ,n j

nG R P dP
(nZ n)
RT 0 P

P ( nZ n) dP

ln i
0
ni P ,T ,n j P

(nZ ) n
Note: Zi and 1
ni ni

P dP
ln i ( Z i 1) (11.60)
0 P
Which comes after integration at constant T and ni
33
The virial equation truncated after 2nd virial
coefficient for a binary gas mixture is given by

34
Fugacity coefficient from the virial EOS
The virial equation: BP
Z 1 (3.38)
(11.61)
RT
the mixture second virial coefficient B: B yi y j Bij
i j
for a binary mixture (B12=B21):
B y12 B11 2 y1 y2 B12 y22 B22 (11.62)
n moles of gas mixture: nBP
nZ n
RT Differentiate w.r.t. n1

(nZ ) P (nB)
Z1 1
n1 P ,T , n2 RT n1 T , n2

Substitute for Z1in Eq. (11.60):

1 (nB) P (nB)
ln 1
P

RT
0 dP
n1 T ,n2
35
RT n1 T ,n
2
 1 (nB) P (nB)
ln 1
P

RT 0
n

1 T , n2
dP
RT

n

1 T , n2

B y12 B11 2 y1 y2 B12 y22 B22

y1 (1 y2 ) B11 2 y1 y2 B12 y2 (1 y1 ) B22
y1 B11 y1 y2 B11 2 y1 y2 B12 y2 B22 y1 y2 B22 (11.62)
y1 B11 y2 B22 y1 y212
n1n2
nB n1 B11 n2 B22 12
n

where 12 2B12 B11 B22 and yi ni / n

ln 1
P
RT
2

B11 y2 12 Similarly: ln 2
P
RT
B22 y1212 (11.63a)
(11.63b)
For multicomponent gas mixture, the general form:

P 1
ln k Bkk yi y j (2 ik ij ) (11.64)
RT 2 i j

where ik 2 Bik Bii Bkk

with ii 0, ij ji for i not equal j 36
Fugacity coefficient from the virial EOS
Note that the above equations are only valid for gases at low
to moderate pressure.
For a binary mixture the fugacity coefficients are given by

For a multicomponent mixture the fugacity coefficients are

given by :

37
Example 11.7: Determine the fugacity coefficients for nitrogen and methane in
N2(1)-CH4(2) mixture at 200 K and 30 bar if the mixture contains 40 mol% N2.
Experimental virial coefficient data are as follows:
B11 = -35.2 cm3/mol, B22 = -105.0 cm3/mol, B12 = -59.8 cm3/mol

3
12 2B12 B11 B22 2(59.8) 35.2 105.0 20.6 cm
mol

ln 1
P
RT

B11 y2212
30
(83.14)(200)

35.2 (0.6) 2 (20.6) 0.0501

1 0.9511

ln 2
P
RT

B22 y1 12
2 30
(83.14)(200)

105.0 (0.4) 2 (20.6) 0.1835

Using Eq. (11.62): B = -72.14 cm3/mol for the mixture

2 0.8324
Using Eq. (3.38): Z = 0.87 for the mixture

38
 11.7 Generalized Correlations for the Fugacity
Coefficient

(11.65) Pr 0
Z 1 ( B B1 )
Pr dPr Tr Pr 0
ln i ( Z i 1) (const. Tr ) ln ( B B1 )
0 Pr Tr

Z Z 0 Z 1
Pr dP Pr dP
PHIB(TR, PR, OMEGA)
ln ( Z 1) r Z 1 r
0
(const. Tr ) For pure gas
0 Pr 0 Pr
or (11.66)
Pr dP Pr dPr
ln ln ln 0 1
with ln
0
( Z 1) r
0
and ln Z 1
1
0 Pr 0 Pr
or ( 0 )( 1 )
For pure gas
See Tables E1:E4 for Z or Tables E13:E16 for 39
Example 11.8: Estimate the fugacity of 1-butene vapor at 200C and 70 bar.

Tr 1.127

Pr 1.731 0 0.627 and 1 1.096

0.191 Tables E15 and E16

ln ln 0 ln 1 0.638 f P (0.638)(70) 44.7 bar

40
 For gas mixture:

P 1

ln k Bkk yi y j (2 ik ij )
RT 2 i j

RTcij
Bij ( B 0 ij B1 ) From Equations (11.69a) (11.69b)
Pcij

Z ci Z cj
3
Tcij (TciTcj ) (1 kij ) V1/ 3
V 1/ 3

Z cij Vcij
ci cj
2 2

Called empirical interaction parameter Z cij RTcij
Pcij
Mixing rules given by Equations (11.70) (11.74)
Vcij

See Prausnitz et al. 1986 i j

ij
2
41
Example 11.9: Estimate 1 and 2 for an equimolar mixture of methyl ethyl
ketone (1) / toluene (2) at 50 C and 25 kPa. Set all kij = 0.

i j Z ci Z cj Z cij RTcij V V
1/ 3 1/ 3 3
ij Z cij Pcij Vcij
ci cj

2 2 Vcij 2

RTcij Tcij (TciTcj ) (1 kij ) 12 2B12 B11 B22
Bij ( B 0 ij B1 )
Pcij

ln 1
P
RT

B11 y2212 0.0128 1 0.987

ln 2
P
RT

B22 y1212 0.0172 2 0.983

See Excel sheet for details of calculations based on given input data

42
Example 11.9: continued

Equimolar mixture of MEK-toluene at

T= 50 oC P= 25 bar
kij = 0 R= 83.14 bar.cm3/mol.K

ij Tcij, K Zcij Vcij, cm3/mol Pcij, bar wij

MEK 11 535.5 0.249 267 41.5 0.323
Toluene 22 591.8 0.264 316 41.1 0.262
Mixture 12 562.95 0.2565 290.812 41.281 0.2925
??
R= 8314 kPa.cm3/mol.K
ij Tr ij B0 B1 Bij, cm3/mol ij 1 2
MEK 11 0.603455 -0.86385 -1.2959 -1375.7931 0
Toluene 22 0.546046 -1.02808 -2.0446 -1872.028 0
Mixture 12 0.574033 -0.94268 -1.6311 -1609.700 28.4211 0.987345 0.982796

ln -0.01274 -0.01735

43
 11.8 The Ideal Liquid Solution Model

Serves as a standard to be compared:

M id xi M iid
(11.79)
(11.75)
Gi Gi RT ln xi
id i
G id xi Gi RT xi ln xi
i i

cf. Giig Giig RT ln yi (11.24)

(11.77) (11.80)
Giid
S
id G
i

R ln xi Siid Si R ln xi S id xi Si R xi ln xi
T T
i
P, x P i i

Vi id Gi id

G
i

Vi id
Vi V id xiVi (11.81)
P T , x P T
i
(11.76)
H id xi H i
H iid Giid TSiid Gi RT ln xi TSi RT ln xi H i
id
Hi i44

(11.78) (11.82)
 The Lewis-Randall Rule
For a special case of species i in an ideal solution:
i i (T ) RT ln fi (11.46) Gi i (T ) RT ln f i (11.31)

i Gi RT ln( fi / f i ) By elimination of i (T )

For ideal solution: iid Giid Gi RT ln( fi id / f i )

But Giid Gi RT ln xi (11.75)

Then, fi id xi f i (11.83)
Using Eqs. (11.52) and (11.34)
Lewis/Randall rule: fi id / xi P f i / P Or, iid i (11.84)
The fugacity coefficient of species i in an ideal solution is equal to the fugacity
coefficient of pure species i in the same physical state as the solution and at the
same T and P. 45
11.9 Excess Properties

The mathematical formalism of excess properties is analogous

to that of the residual properties:
M E M M id (11.85)
M represents the molar (or unit-mass) value of any extensive
thermodynamic property (e.g., V, U, H, S, G, etc.) For
example, nG E nV E nH E G
E
d dP 2
dT i dni (11.89)
RT RT RT i RT

which is the fundamental excess-property relation.

See Table 11.1 for a summary of equations for the Gibbs
energy and related thermodynamic properties.

46
47
Example 11.10: (a) If CPE is a constant, independent of T, find expression for GE, SE,
and HE as functions of T. (b) From the equations developed in part (a), find values
for GE , SE and HE for an equimolar solution of benzene(1)/n-hexane(2) at 323.15 K,
given the following excess-property values for equimolar solution at 298.15 K: CPE =
-2.86 J/mol.K, HE = 897.9 J/mol, and GE = 384.5 J/mol
2G E 2G E a
From Table 11.1: C T
E

T T
P 2 2
P , x CPE a const. P, x T
By integration
G E G E
From Table 11.1: S
E
a ln T b
T P,x T P, x
By integration By integration
S E a ln T b G E a(T ln T T ) bT c

H E G E TS E aT c

CPE a 2.86 897.9 a(298.15) c Solve for the values of a, b

and c and hence calculate
384.5 a[298.15 ln(298.15) 298.15] b(298.15) c the excess properties at
48
323.15 K
Example 11.10: continued

a -2.86
b -18.0161 Goal seek
c 1750.309 6.82E-13
Given:
@ 298.15 SE 1.720946
GE 384.5 384.5
HE 897.6 897.5

@ 323.15 SE 1.490659
GE 344.3936
HE 826.1

49
The excess Gibbs energy and the activity
coefficient
The excess Gibbs energy is of particular interest:
G E G G id
Gi i (T ) RT ln fi

Giid i (T ) RT ln xi f i

fi The activity coefficient of species i in

Gi Gi Gi
E id
RT ln solution. A factor introduced into
xi f i
Raoults law to account for liquid-phase
fi non-idealities.
i
xi f i (11.90)

Gi E RT ln i (11.91) Gi E 0, i 1

c.f. Gi R RT ln i For ideal solution 50

 nG E nV E nH E Gi
E
d dP 2
dT dni Excess Property Relations
RT RT RT i RT

nG E nV E nH E
d dP 2
dT ln i dni (11.93)
RT RT RT i

V E (G E / RT )

RT P T , x
Experimentally accessible values:
H E
(G / RT )
E
T VE and HE values come from mixing experiments.
RT T P, x Activity coefficients from VLE data.
(nG E / RT ) (11.94) (11.96)
ln i
ni P ,T ,n j

GE
xi ln i
RT i
(11.99) These equations are important in phase-
x d ln
i
i i 0 (const. T , P) (11.100) equilibrium thermodynamics.

51
 ( nG R
/ RT )
At T and P we have ln i (11.59)
ni P ,T ,n j

By analogy: (11.97)

(11.98)

These equations allow calculation of the effect of T and P on the activity

coefficient.

52
The nature of excess properties
GE: through reduction of VLE data
HE: from mixing experiment
SE =(HE - GE)/T

From Figure 11.4: Excess properties at 50 oC for six binary liquid systems :
(a) chloroform/n-heptane; (b) acetone/methanol ; (c) acetone/chloroform;
(d) ethanol/n-heptane; (e) ethanol/chloroform; (f) ethanol/water
Excess properties become zero as either species becomes pure (x~ 1).
GE is approximately parabolic in shape; HE and TSE exhibit individual
composition dependence.
The extreme value of the excess properties often occurs near the
equimolar composition (x~ 0.5).

53
Fig. 11.4* Molar volume change of mixing for solutions of cyclohexane (1)
with some other C6 HCs (Perrys Chemical Engineers Handbook (7th ed.),
McGraw Hill, 1997. 54
Figure 11.4: Excess properties at 50 oC for six binary liquid systems: Property changes of mixing at
50C for 6 binary liquid systems: (a) chloroform(1)/n-heptane(2); (b) acetone(1)/methanol(2); (c)
acetone(1)/ chloroform(2); (d) ethanol(1)/n-heptane(2); (e) ethanol(1)/chloroform(2); 55
(f) ethanol(1)/water(2).
Fig. 11.4** Property changes of mixing at 50C for 6 binary liquid systems:
(a) chloroform(1)/n-heptane(2); (b) acetone(1)/methanol(2); (c) acetone(1)/ chloroform(2); (d)
ethanol(1)/n-heptane(2); (e) ethanol(1)/chloroform(2); (f) ethanol(1)/water(2). (Perrys Chemical
Engineers Handbook (7th ed.), McGraw Hill, 1997.
56